Substituted phenyl compounds and processes for preparing the same

ABSTRACT

Substituted phenyl compounds endowed with chain extension activity for formulations such as polyurethanes are disclosed, and which have the general formula: ##STR1## wherein n is 1-1000 and m is 1-100; and R 1  and R 2  are each independently selected from the group --C 2  H 4  -- and --C 3  H 6  --; and R 3  is from the group consisting of: ##STR2## and the diasteromeric salts thereof.

This application is a Continuation-In-Part of patent application Ser.No. 08/070,144, filed May 28, 1993, issued as U.S. Pat. No. 5,346,983.

BACKGROUND OF THE INVENTION

1. Field of the Invention

The present invention relates to novel derivatives of4-hydroxyacetophenone (4-HAP) to processes for preparing them, topolymer compositions which contain the novel compounds, and to the useof said compositions for a wide variety of end use applications.

2. Description of Related Art

The following prior art references are disclosed in accordance with theterms of 37 CFR 1.56, 1.97, and 1.98.

U.S. Pat. No. 5,169,848, issued Dec. 8, 1992, to Bettarini et al.,discloses new pyridazinones endowed with insecticidal and acaricidalactivity.

U.S. Pat. No. 3,520,931, issued Jul. 21, 1970, to d'Ostrowick et at.,discloses a process for resolving a mixture of optical antipodes of aprimary alpha-arylalkylamine in which one of these antipodespredominates.

U.S. Pat. No. 5,011,996, issued Apr. 30, 1991, to Kiel et al., disclosesreaction products of oxo compounds and amines or ammonia, such asα-(p-Cholorophenyl)-ethylamine (Example 1 therein).

U.S. Pat. No. 4,394,496, issued Jul. 19, 1983, to Paul G. Schrader,discloses polyglycidyl ethers of these (hydroxyphenyl) alkanes, theirblends with other epoxy compounds, and their cured products.

U.S. Pat. No. 4,388,250, issued Jun. 14, 1983, to Farbet et al.,discloses a process for the preparation of p-Hydroxybenzyl-nitrites(note Table I, columns 7 and 8).

Other U.S. patents which have related application and may be of interestinclude U.S. Pat. Nos. 2,298,284; 3,366,684; 3,739,026; 3,225,098;3,928,603; and 5,047,592.

All of the above-cited prior an patents are incorporated herein byreference in their entirety.

3. Additional Background Information

Compounds belonging to the class of hydroxyacetophenones, processes forpreparing the same, and their end use applications are disclosed in U.S.Pat. Nos. 4,663,485; 4,524,217; 4,933,496; and 4,994,613, the entiredisclosures of which patents are incorporated herein by reference.

SUMMARY OF THE INVENTION

The present invention provides novel substituted phenyl compounds("SPC") endowed with chain extension activity for formulations such aspolyurethanes and which have the general formula: ##STR3## wherein n is0-1000; and R₁ and R₂ are from the group --CH₂ --CH₂ --; --CH₂--C(CH₃)H--; and --C(CH₃)H--CH₂ --; and R₃ from the group consisting of:##STR4## and the diasteromeric salts thereof.

DETAILED DESCRIPTION OF THE PREFERRED EMBODIMENTS

The present invention provides novel substituted phenyl compounds (SPC)which are derivatives of 4-hydroxyacetophenone, a well-known basicbuilding block for numerous organic compounds. These novel SPC's havethe general formula as follows: ##STR5## wherein: n is 0 to 1000(preferably 0 to 100);

R₁ equals R₂ ;

R₁ and R₂ represent a member from the group:

--CH₂ --CH₂ --

--CH₂ --C(CH₃)H--

--C(CH₃)H--CH₂ --; and

R₃ is from the group: ##STR6##

The compounds having the general formula (I) can be prepared by reactingan alkali metal salt of 4-hydroxyacetophenone (4-HAP) with an oxidematerial such as ethylene oxide or propylene oxide in the presence of asuitable catalyst to form the novel SPC having the above formula (I).This overall reaction scheme using ethylene oxide is shown as follows:##STR7##

In equation (A), M is an alkali metal such as potassium. In equation(B), X represents the number of molar equivalents of the ethylene oxide(or propylene oxide) is used to form the chain, and N+1 equals X. n canbe 0 to 1000, but are preferably from 0 to 100.

In the formulation of the alkali metal salt of 4-HAP, equation (A), thereactants are mixed together in a reaction vessel along with a suitableinert solvent such as isopropanol and then heated at about 30° C. toabout 100° C. for a sufficient period of time until all the solids aredissolved into the liquid. The resultant reaction mass is then allowedto cool to room temperature and then the desired alkali metal salt isallowed to crystalize over a period of time suitable to promotecrystallization from the solution. The solid material, i.e. the 4-HAPsalt, is then separated from the mother liquor by any conventionalmeans, such as filtration. The solid material is then washed with asuitable inert solvent such as heptane and then dried at a temperatureof from about 30° C. to about 100° C., under vacuum, where so desired.

In conjunction with equation (B) above, the alkali metal salt of 4-HAPis charged into a reaction vessel along with pre-selected quantities ofeither ethylene oxide or propylene oxide and a suitable inert solventsuch as dimethylformamide (DMF). The reaction vessel is provided with acondenser and a mechanical stirrer. The reaction mass is then slowlyheated from room temperature (i.e. 20° C.) to about 100° C. over aperiod of time to insure that the ethoxylafion of propoxylation takesplace in the desired fashion. While this part of the process isconducted at atmospheric pressure, it is within the scope of the presentinvention to conduct this reaction under pressure, e.g. from about 20psig to about 300 psig, and thus reduce the reaction times. After thereaction has taken place, the reaction mass is allowed to cool to roomtemperature and then a suitable de-salting agent, such as acetic acid,is added to this mass in order to remove and inactivate the alkali metalion. This ion complex precipitates and the resultant suspension isseparated from the mother liquor by any conventional means such asfiltration. This liquid is then reduced under vacuum to an oil, and theoil is then distilled under vacuum and the fraction boiling between 130°C. and 210° C. is collected and represents the desired end product, i.e.the ethoxylated or propoxylated 4-HAP.

Referring to equation (B), it was unexpectedly found that the reactionproduces two separate materials which can be recovered by anyconventional means such as distillation.

The substituted phenyl compounds (SPC) of this invention areparticularly suited for reaction with isocyanates to manufacturearticles by a Reaction Injection Molding (RIM) process. RIM is atechnique for the rapid mixture and molding of large, fast-curingurethane parts. RIM polyurethane parts are used in a variety of exteriorbody applications on automobiles where the light weight contributes toenergy conservation. RIM parts are generally made by rapidly mixingactive hydrogen-containing materials with polyisocyanate and placing themixture into a mold where reaction proceeds. After reaction andde-molding, the parts may be subjected to an additional curing stepwhich comprises placing the parts in an oven, held at 250° F. or higher.

Surprisingly, it also has been found that the substituted phenylcompounds of this invention are useful as curing agents in forming clearepoxy castings and adhesives with highly satisfactory physicalproperties. Such epoxy products find application in the electrical andelectronic fields. These SPC's also have been found to be suitable foruse in polyamides, polyesters, polycarbonates, and epoxy resins.

The following specific examples are supplied for the purpose of betterillustrating the invention. These examples are not intended, however, tolimit or restrict the scope of the invention in any way and should notbe construed as providing conditions, parameters, or values which mustbe utilized exclusively in order to practice the present invention.

EXAMPLE 1 Synthesis of Potassium Salt of 4-Hydroxyacetophenone

A mixture of 4-hydroxyacetophenone (556 g), potassium hydroxide (273 g),and isopropanol (3 L) is charged to a 5 L glass reactor fitted with acondenser and mechanical stirrer. The mixture is heated until all of thesolids are dissolved (80° C.). The solution is then cooled to roomtemperature and the product is allowed to crystallize for 12 hours. Thesolid is isolated by filtration, washed with heptane (1 L), and driedunder vacuum (60° torr., 50° C.). The product is a light yellow solidand weighs 610 g (86%). This reaction is representative of equation (A)above.

EXAMPLE 2

A mixture of potassium 4-acetyl phenolate (313 g), propylene oxide (507g), and DMF (900 mL) is charged to a 3 L glass reactor fitted with acondenser and a mechanical stirrer. The reaction is heated and thetemperature slowly increases from 52° C. to 82° C. over a period ofthree hours. The mixture is cooled to room temperature and acetic acid(108 g) is slowly added. The suspension is filtered and the filtrate isreduced under vacuum to an oil. The oil is distilled under vacuum (0.5tort.) and the fraction boiling between 140° C. to 205° C. is collected.The product is a clear, colorless liquid and weighs 284 g (63%). Typicalphysical properties are given in Table I. This reaction isrepresentative of equation (B) above, except that propylene oxide isused instead of ethylene oxide.

                  TABLE I                                                         ______________________________________                                        Typical Properties of Propoxylated 4-Hydroxyacetophenone                                         Propoxylated                                               Property           4-Hydroxyacetophenone                                      ______________________________________                                        Average n          (wt %)                                                     n = 0               12.58                                                     n = 1               76.08                                                     n = 2               11.34                                                     n = 3               --                                                        Molecular Weight (Average)                                                                       251.28                                                     Boiling Range      140-193° C. (<1 torr.)                              Density (@ 27° C.)                                                                        1.094 g/mL                                                 Color              Clear, Colorless Liquid                                    Solubility (>5 wt %)                                                          Water              No                                                         Acetone            Yes                                                        Methanol           Yes                                                        N,N-Dimethylformamide                                                                            Yes                                                        Heptane            No                                                         Ethyl Acetate      Yes                                                        ______________________________________                                    

EXAMPLES 3-18

Using the procedures set forth in Examples 1 and 2 above, the compoundsreported in Table II are obtained. It is inherent that isomers of thepropyl group are formed; however, NMR indicates that the indicatedcompounds are formed.

                  TABLE II                                                        ______________________________________                                         ##STR8##                                                                     Example                                                                              R.sub.1 /R.sub.2                                                                              n (Average)                                                                              R.sub.3                                     ______________________________________                                        3      CH.sub.2CH.sub.2                                                                              2          C(O)                                        4      CH.sub.2CH.sub.2                                                                              13         C(OH)H                                      5      CH.sub.2CH.sub.2                                                                              81         C(O)                                        6      CH.sub.2CH.sub.2                                                                              4          C(O)                                        7      CH.sub.2CH.sub.2                                                                              3          C(OH)H                                      8      CH.sub.2CH.sub.2                                                                              6          C(OH)H                                      9      CH.sub.2CH.sub.2                                                                              10         C(OH)H                                      10     CH.sub.2CH.sub.3                                                                              4          C(O)                                        11     CH.sub.2C(CH.sub.3)H                                                                          5          C(O)                                        12     CH.sub.2C(CH.sub.3)H                                                                          5          C(OH)H                                      13     CH.sub.2C(CH.sub.3)H                                                                          9          C(OH)H                                      14     CH.sub.2C(CH.sub.3)H                                                                          5          C(OH)H                                      15     CH.sub.2C(CH.sub.3)H                                                                          5          C(O)                                        16     CH.sub.2C(CH.sub.3)H                                                                          11         C(O)                                        17     C(CH.sub.3)HCH.sub.2                                                                          3          C(OH)H                                      18     C(CH.sub.3)HCH.sub.2                                                                          3          C(O)                                        ______________________________________                                    

EXAMPLE 19 Synthesis of a Polyurethane with SPC

A 2.0 g sample (0.012 mole) of tolylenediisocyanate (a 80:20 mixture of2,4 and 2,6 tolylenediisocyanate) is mixed carefully with a 2.9 g sample(0.011 mole) of the SPC prepared according to the procedure in Example 2above. The mixture thickens and hardens to a glassy resin with thegeneration of heat. The material is a hard, clear, amber solid and isfound to be suitable for use in automobile parts.

EXAMPLES 20-36 Preparation of Polyurethanes Containing SPC

Polyurethanes are prepared incorporating SPC by substitution of SPC forother polyols present in a reaction mixture. Examples are described inthe Encyclopedia of Polymer Science & Engineering, Volume 1, pgs.243-303 (2nd Edition, 1988, John Wiley & Sons). As used herein, theterm, "polyurethane" refers to materials that include the carbamatefunction as well as other functional groups such as ester, ether, amide,and urea. Polyurethanes are usually produced by the reaction of apolyfunctional isocyanate with a polyol or other hydroxyl-containingreactant. Since the functionality of the hydroxyl-containing reactant orthe isocyanate can be adjusted, a wide variety of branched orcross-linked polymers can be formed. The hydroxyl-containing componentmay be of a wide variety of molecular weights and types includingpolyester and polyester polyols. The polyfunctional isocyanates may bearomatic, aliphatic, cycloaliphatic, or polycyclic in structure and canbe used directly as produced or modified. The flexibility in reactantsleads to the wide range of physical properties of available materials.Present invention polymers are prepared by substituting SPC for aportion of the hydroxyl-containing reactant in a mole ratio ofSPC/hydroxyl from about 0.001:1 to about 1:1 for the polyol in apolyurethane reaction mixture, or, in other words, from about 0.05 toabout 50 mole percent of the total mixture as described above inconnection with Example 19. Specifically, Example 19 is repeated usingthe SPC compounds from Examples 3-18. The resultant polyurethanecompositions are found functional in a wide variety of automobile parts.

In conjunction with the novel SPC compounds falling within the generalstructural formula (I) above, each of these compounds contains a chiralcarbon atom and, consequently, is a racemate which consists of twomirror-image forms (enantiomers). Where one so desires to provide and/oruse only one or single enantiomer thereof, it is within the scope of thepresent invention that this can be accomplished by means well-known inchirotechnology such as optical resolution by known resolving agentssuch as optically pure chiral acids. Examples of chiral acids include,without limitation thereof, tartaric acid, molic acid, camphorsulfonicacid, lactic acid, bromocamphorsulfonic acid, mandelic acid,2-(4-isobutyl-phenyl)-propionic acid (ibuprofen), and derivativesthereof. The use of these chiral acids with the novel SPC provides thediasteromeric salts thereof. Additional general information onchirotechnology may be found in Enantiomers, Racemates, and Resolutions,Jacques et al., Krieger Publishing Company (Malabar, Fla.) 1991 andwhich is incorporated herein by reference in its entirety.

In another facet of the present invention, there is provided novelcompounds and processes for preparing the same where one so desires to"end-cap" the polymer chain. In the polymer art, e.g., see Encyclopediaof Polymer Science & Engineering, Supplement Volume--1990, page 408,.John Wiley & Sons (New York) and which book is incorporated herein byreference in its entirety; there are numerous reasons to "end-cap" thechain, e.g. to prevent decomposition. Thus, in this part of the presentinvention, there are provided the following novel end-capped compounds:

I. Substituted phenyl compounds having the structural formula: ##STR9##wherein n is 1-1000 and m is 1-100; and R₁ and R₂ are each independentlyselected from the group consisted of --C₂ H₄ -- and --C₃ H₆ --; and R₃is from the group: ##STR10## and the diasteromeric salts thereof.Compounds falling within formula (A) above include, without limitation,(B) and (C) below.

II. Substituted phenyl compounds having the structural formula:##STR11## wherein n is 1-1000 and m is 1-100; and R₁ is from the groupconsisting of: ##STR12## and the diastereomeric salts thereof. III.Substituted phenyl compounds having the structural formula: ##STR13##wherein n is 1-1000, m is 1-100; and R₁ is from the group consisting of:##STR14## and the diasteromeric salts thereof.

In formulae (A), (B), and (C) above, m is an integer from about 1 toabout 100, preferably from about 1 to about 10, and represents the"end-capping" function of the polymer. The end-capping of the polymer isaccomplished by contacting the initial reaction mixture (after reaction)with either ethylene oxide or propylene oxide. This is illustrated bythe following example which is basically a repeat of Example 2.

EXAMPLE 37

A mixture of potassium 4-acetyl phenolate (313 g), propylene oxide (507g), and DMF (900 mL) is charged to a 3 L glass reactor fitted with acondenser and mechanical stirrer. The reaction is heated and thetemperature slowly increases from 52° C. to 82° C. over a period ofthree hours. At the end of this time, ethylene oxide (406 g) iscontacted with the initial reaction mixture for a period of 30 minutes.The overall mixture is cooled to room temperature and acetic acid (108g) is slowly added. The suspension is filtered and the filtrate isreduced under vacuum to an oil. The oil is distilled under vacuum (0.5torr.) and the fraction boiling between 140° C. to 205° C. is collected.The product is a clear, colorless liquid and weighs 288 g (64%). Thephysical properties are similar to those in Table I except that m is 1.5(average).

What is claimed is:
 1. Substituted phenyl compounds having the formula:##STR15## wherein n is 1-1000 and m is 1-100; and R₁ and R₂ are eachindependently selected from the group consisting of --C₂ H₄ -- and --C₃--H₆ --; and R₃ is from the group: ##STR16## and the diasteromeric saltsthereof.
 2. Substituted phenyl compounds having the structural formula:##STR17## wherein n is 1-1000, m is 1-100; and R₁ is from the groupconsisting of: ##STR18## and the diasteromeric salts thereof. 3.Substituted phenyl compounds having the structural formula: ##STR19##wherein n is 1-1000 and m is 1-100; and R₁ is from the group consistingof: ##STR20## and the diasteromeric salts thereof.
 4. The compound asset forth in claim 1 wherein R₃ is: ##STR21##
 5. The compound as setforth in claim 1 wherein R₃ is: ##STR22##
 6. The compound as set forthin claim 2 wherein R₁ is: ##STR23##
 7. The compound as set forth inclaim 2 wherein R₁ is: ##STR24##
 8. The compound as set forth in claim 3wherein R₁ is: ##STR25##
 9. The compound as set forth in claim 3 whereinR₁ is: ##STR26##